Charge transfer complexes of tetrakisamino ethylenes



United States Patent a corporation of Delaware No Drawing. Filed Feb. 27, 1961, Ser. No. 91,590 34 Claims. (Cl. 260-246) This application is a continuation-in-part of my copending application Serial No. 836,062, filed August 26, 1959, and now abandoned.

This invention relates to, and has as its chief object provision of, novel charge transfer complexes of tetrakis (disalkylamino)ethylenes with pi or Lewis acids.

Complexes between Lewis acids and Lewis bases of Widely varying structures have long been known. In many instances, one or both the acid and base components are organic, and frequently aromatic, in nature. In all but the rarest instances wherein one or both of the components is or are organic in nature the multiple linkage, from which arise the pi orbitals used in forming the complex, is part of a classically resonating multiple bond system.

This invention is generic to the charge transfer compounds or complexes of tetrakis(dialkylamino)ethylenes with Lewis acid compounds generically, i.e., with electron acceptors. The aminoethylenes are Lewis bases or electron donors. The literature shows various complexes from mixtures of Lewis acids and Lewis bases (but not involving the aminoethylenes). Many such complexes have been referred to as pi complexes. More recently, the concept that they are charge transfer complexes has become acceptedsee Mulliken, J. Am. Chem. Soc. 74, 811 (1952). It is believed more nearly proper to use the generic term charge transfer compounds or complexes free of the pi connotation since, while many of these complexes owe their existence to bondings involving pi orbitals, charge transfer complexes do exist which do not involve pi orbitals. This terminology is believed proper even as applied to the diamagnetic complexes in which maximum charge transfer occurs not in the ground electronic state but in the excited state-see Orgel, Quart. Rev. Chem. Soc. 8, 422 (1954).

It has now been discovered that the tetrakis(dialklyamino)ethylenes, which are not aromatic, and, furthermore, in which the multiple carbon-carbon linkage is not part of a classically resonating multiple bond system, not only form charge transfer complexes with organic pi or Lewis acids, but also that these complexes are extremely stable and can be handled readily even at elevated temperatures. Generally the complexes with the best properties will be colored and these are preferred.

Any pi or Lewis acid can be used to form the present charge transfer complexes of the tetrakis(dialkylamino) ethylenes. Generally speaking, such Lewis acids are molecules with unfilled octets such as triphenyl boron or are unsaturated organic compounds. 'A preferred class are those unsaturated organic compounds containing one or more carbon-carbon multiple bonds. A particularly preferred class of such pi acids are those containing bonded to at least one of the multiply bonded carbon atoms at least on radical selected from the group consisting of nitro, nitroso, nitrile, carbacyl, trihalomethyl, 1,1-dihaloalkyl, perhaloalkyl, phenyl, a-substit uted-phenyl, naphthyl, sulfonyl, azo, and the like. Suitable specific examples include: dimethyl azodicarboxylate, methyl vinylsulfone, a-nitro-fi-furylethylene, p-dinitrosobenzene, diethyl acetylenedicarboxylate, fu maronitrile, maleonitrile, p-diacetylbenzene and a,a,a,a,a,a-hexachloro-p-xylene.

This present invention is generic to the addition com- Patented Mar. 8, 1966 pounds of tetrakis(dialkylamino)ethylenes with unsaturated organic compounds, and perferably with organic compounds containing one or more carbon-carbon multiple bonds. Particularly preferred are the colored paramagnetic addition compounds of these tetrakis(dialkylamino)ethylenes with organic compounds containing one or more carbon-carbon multiple bonds wherein the said addition complexes or compounds are characterized as melting above C. and exhibiting a spectral absorption in the range 0.5 to 4.0 microns. An especially preferred group of the colored paramagnetic addition compounds of the present invention are those compounds further characterized as containing the tetrakis(dialkylamino)ethylenes and the organic compound exhibiting pi acid character in combined molar ratios between 1:1 and 1:10. The most preferred class of these colored addition compounds of the tetrakis(dialkylamino)ethylenes with Lewis acids are those which are paramagnetic, which melt above 100 C., which are soluble to the extent of less than 0.1% in hexane, which exhibit the above spectral characteristics, wherein the said tetrakis (dialkylamino)ethylene and Lewis acid are, respectively present in mole ratios between 121 and 1:10 and the Lewis acid contains one or more carbon-carbon multiple bonds with at least one of the multiply bonded carbon atoms bonded to at least one radical selected from the group consisting of nitro, nitroso, nitrile, carbacyl, trihalomethyl, 1,1-dihaloalkyl, perhaloalkyl, halo, phenyl, tat-substituted phenyl, naphthyl, sulfonyl, azo, and the like.

The invention is generic to the colored addition compounds of tetrakis(dialkylamino)ethylenes with organic pi or Lewis acids. The alkyl substituents can be straight chain or branched chain and can vary widely in the number of carbons present therein. The structure for these aminoethylenes can be represented as follows:

RIIEN I/ wherein the R"s which can be alike or different and taken pair-wise on each individual nitrogen or on adjacent nitrogens together joined, are used to represent alkyl and oxa and aza interrupted alkyl radicals of 1 to 10 carbons each and preferably no more than 5 carbons which can be joined pairwise as above to form 3 to 7 membered heterocycles. Suitable further illustrative examples include: tetrakis( diethylaminoy ethylene, tetrakis (ethylmethylamino ethylene, tetrakis (N- piperidino)ethylene, tetrakis(N pyrrolidinyDethylene, tetrakis(mo-rpholino)ethylene, tetrakis[N-(N' methyl)- piper-azinyl] ethylene, tetrakis (dimethylaminomethyleneamino)ethylene, 1,1,3,3' tetramethyl-A -bi(imidazolidine), 1,1,3,3'-tetraethyl-A '-bi(imidazolidine), 1,3-d-iethyl-1',3-dirnethyl-A -bi(imidazol-idine) 1,1',3,3-tetramethyl-A bi(hexahydropyrimidine), and the like.

The following examples in which the parts given are by weight are submitted to further illustrate the invention but not to limit it.

Example I Under an atmosphere of nitrogen a solution of 0.344 part of tetrakis(dimethylamino)ethylene (T MAE) in 35 parts of 1,2-dimethoxyethane was added dropwise with stirring to a solution of 1.27 parts (3.0 molar proportions based on TMAE) of chloranil in 85 parts of 1,2-dimethoxyethane. A microcrystalline, dark green solid separated which was removed by filtration and subsequently air-dried. There was thus obtained 1.3 parts (81% of theory) 1/3TMAE/chloranil charge transfer compound as dark green crystals which, on heating, exhibited a color change to brown at temperatures above C. Electron paramagnetic resonance analysis showedthe compound to be paramagnetic, Le, a strong EPR absorption was evidenced. The resistivity of the compound was found to be 8.9)( ohm cm. at 25 C.

Analysis.-Calcd. for 1/3TMAE/chloranil Example 11 Under an atmosphere of nitrogen a solution of 0.86 part of TMAE in 67 parts of methylene dichloride was added dropwise with stirring over a period of 2.5 hours to a solution of 3.64 parts (an equimolar proportion'based on the TMAE) of b-romanil in 670 parts of methylene dichloride. A bright green solid formed which was removed by filtration, and after air-drying there was thus obtained 4.13 parts (92% of theory) of the 1/2TMAE/ bromanil charge transfer compound as bright green crystals which upon being heated to 180 C. changed to a tan color and on continued heating finally decomposed at 220-230 C. The compound was paramagnetic and errhibited a strong EPR absorption. The resistivity was 2.9 X 10 ohm cm. at 25 C.

Analysis.Calcd. for 1/ 2TMAE/ b-romanil 22 24 'a 4 4) I C, 25.2%; H, 2.3%; Br, 61.0%. Found: C, 25.1%; H, 2.1%; Br, 60.8%.

The infrared spectrum, asobtained onan oil mull of the compound, exhibited maxima at 1675, 1672 (doublet), 1550, 1500, 1400, 1260, 1210, 1180, 1140, 1100, 955, 875, and 718 cm. The strong bands at 1063, 1050, 870, and 700 cm. present in the infrared spectrum or bromanil itself are absent in the spectrum of the compound. patterns made with the solid compound on paper were ac- Image curately copied by the method described in Example I.

Example Ill Under an atmosphere of nitrogen a solutionof 0.172 part of TMAE in 40 parts of acetone was added dropwise with stirring to asolution of 0.526 part (one molar pro- Under an atmosphere of nitrogen a solution of 0.172 partof TMAE in 54 parts of methylene dichloride was added dropwise to a solution, with stirring, of 1.1 parts (10 molar proportions based on the TMAE) of tetracyanoethylene (TCNE) in 270 parts of methylene dichloride. The resultant brownish-black precipitate was isolated by rapid filtration and driedunder reducedpressure. brownish-black TMAE/TCNE charge transfer compound exhibited a strong EPR absorption and, therefore, was paramagnetic, The resistivity at 25. C. was 8.9)(10 ohm cm.

Found: C, 20.0%; H,

The-

4 Example V Under an atmosphereof nitrogen a solution of 0.172 Q part of TMAE in 67 parts of methylene dichloride was added dropwise with stirring to a solution of 0.364 part (an equirnolarproportion based on the TMAE) of tetrabromo-1,2-benboquinone iny134 parts of "methylene di- 7 chloride. The resultant precipitate was isolated by filtration, and after air-drying there was. thus obtained. the

transfer;- compound as a light brown solid which decomposed above 250 C. and exhibited astrong EPR'absorption, i.e., was

TMAE/tetrabromo-1,2-benzoquinone charge I paramagnetic.

Example Vl Under an atmosphere of nitrogen a solution of 0.172 part of TMAE in 28 parts of benzene'was added-dropwise with stirring to a solution of 0.158 part (an equirnolar proportion based on the TMAE) of diphenoquinone in 160 parts of benzene. The resultant precipitate, was 'removed by filtrati-on,'and after air-dryingthere was thus obtained 0.25jpart1 TMAE/diphenoquinone .charge transfer compound as a light tan solid which exhibited an unusually wide EPR absorption. The resistivity of the compound was 6.8 X10 ohm cm. at25 C.

Example. VII

Under an atmosphere of nitrogen, a solution of 0.361

part of m-dinitrobenzene in 8 parts of benzene was added dropwise with stirringto a solution of 043- part (an equimolar proportion based on the dinitrobenzene) of TMAE, in 16 parts of benzene The resulting purple solution'of the TMAE/m-dinitrobenzene charge transfer compound was paramagnetic, i.e., exhibited .an EPR.

absorption; The same preparation carried outzinmethylene dichloride instead of benzene afforded a red, diamagnetic solution.

Example VIII Under an atmosphere of nitrogen a solution of 0.98 part of TMAE in 107 parts of methylene dichloride wasadded dropwise with stirring over a period of 3-4 hours to a 7 solution of 1.36 parts (slight excess over. an equimolar proportion based on the :TMAE) of hexachlorocyclopentadiene int134 parts of methylene dichloride.- The solution became dark green in color, changing to a deep brown as a deep brown solid precipitated. This was removed 1 by filtration, and after air-drying there was thus obtained- 1.53 parts of the 1/1 TMAE/hexachlorocyclopentadiene charge transfer compound as a deep brown solid. The

product was paramagnetic andexhibited EPR absorption.

Analysin-Calcdfor a 1/1 TMAE/hexachlorocyclo- 1 pentadiene-compound .(C H 4N Cl C, 38.3%; H, 5.1%;N,11.8%. Foundr'C;38.0%;H,5.2%;N,.11.9%.

Example IX In "an atmoshpere of nitrogen a solution of 1.3 8 parts of TMAE in 107 parts of methylene dichloride wasadded dropwise withstirring over a period of 2 to 3 hours to a solutionof one part. (an equimolar proportion based on the TMAE) of dichlorofumaronitrile in 134 parts of, meth- Y ylene dichlorideLi A-brownish-blackprecipitate. formed.

immediately. After stirring the .reaction mixture overnight, the precipitate was removed by filtration, and after? air-drying there was thus obtained 2.03 parts of theory) of a 1/1 TMAE/'dichlorofumaronitrile.charget transfer compound as a brown-black solid. The product; exhibited an. EPR absorption,- i.e.,' was paramagnetic.. The resistivity of the product at 25 C. was-1.57 10 ohm cm.

Example X Example XI Under an atmosphere of nitrogen 21 solution of 0.344 part of TMAE in 27 parts of methylene dichloride was added dropwise with stirring to a solution of 0.276 part (an equimolar proportion based on the TMAE) of indane- 1,2,3-trione in 200 parts of methylene dichloride. The resultant precipitate was isolated by filtration under nitrogen, and, after vacuum drying, the 1/ 2 TMAE/indane- 1,2,3-trione charge transfer compound was obtained as a black, hygroscopic solid. The charge transfer compound exhibited an intense EPR absorption, i.e., was intensely paramagnetic.

Analysis. Calcd for 1/ 2 TMAE/indanetrione (C H N O N, 10.8%. Found: N, 10.8%.

Example XII 2,4,7-trinitro-9-fluorenone charge transfer compound as a black, fiutfy solid. The product was paramagnetic and exhibited EPR absorption.

Analysis.Calcd. for 1/ 3 TMAE/2,4,7-trinitro-9-fiuorenone (C49H39N13O21): N, Found: N,

Example XIII In a glass reactor fitted with a short packed distillation column, condensing means, and a distillation takeoff head, a mixture of 119 parts of a,a-dimethoxytrimethylamine and 142 parts of anhydrous pyrrolidine was heated under reflux in an oil bath at 851 06 C. Over a four-hour period 33 parts of dimethylamine was collected in a cold trap connected to the still. Methanol was then removed by distillation from the mixture as the temperature of the oil bath was slowly raised over a three-hour period to 212 C. and held at ZOO-212 C. for two hours. A total of 66 parts of methanol was obtained. On cooling to 90 C. the reaction residue crystallized. There was thus obtained 149.5 parts (98% of theory) of tetrakis(N-pyrrolidinyl)ethylene which after crystallization from acetonitrile was obtained as white needles melting at 91-93" C., fiuorescing under ultraviolet light (3660 A.), and chemiluminescing on exposure to air.

Analysis.-Calcd. for C H N C, 71.0%; H, 10.6%; N, 18.4%. Found: C, 71.2%; H, 10.6%; N, 18.5%.

Under an atmosphere of nitrogen a solution of 0.30 part of tetrakis(N-pyrrolidinyl)ethylene in 17 parts of 1,2-dimethoxyethane (so-called glyme) was added dropwise with stirring over a period of 30 minutes to a solution of 1.0 part (2.36 molar proportions based on the amine) of bromanil in 86 parts of glyme. The resulting precipitate was isolated by filtration and air-dried. There was thus obtained 0.90 part of the tetrakis(N-pyrrolidinyl)ethylene/bromanil charge transfer compound as a dark yellowish-green solid which decomposed above 207 C. and exhibited a strong EPR absorption, i.e., was paramagnetic. Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

In the same manner there was obtained from 0.76 part of tetrakis(N-pyrrolidinyl)ethylene in 18 parts of tetrahydroiuran and 1.02 parts (two molar proportions based on the amine) of 7,7,8,8 -tetracyanoquinodimethane (TCNQ) in 89 parts of tetrahydrofuran, after filtration and drying, 1.77 parts of the tetrakis(N-pyrrolidinyl)- ethylene/TCNQ charge transfer compound as a bluishblack solid decomposing above 185 C. and exhibiting a strong EPR absorption. Image patterns made with the solid charge transfer compound were easily and accurately copied by the method described in Example I.

Example XIV A mixture of 59.5 parts of a,ot-dimethoxytrimethylamine and 170 parts (2.0 molar proportions based on the amine) of anhydrous piperidine in a glass reactor was attached to a still as in Example XIII and was heated at the reflux in an oil bath until evolution of dimethylamine ceased. Methanol was then distilled from the reaction mixture as the temperature of the heating bath was slowly raised over a period of eight hours to C. A total of 31.6 parts (theory, 32 parts) of methanol was obtained. Removal of all material (including excess piperidine) volatile below a bath temperature of C., while maintaining the reactor at a pressure corresponding to 0.55 mm. of mercury, atforded 80 parts (89% of theory) of tetrakis(piperidino)ethylene as a residue which crystallized on cooling. After recrystallization from acetonitrile, the product melted at 5961 C.

Analysis.-Calcd. for C H N C, 73.3%; H, 11.2%; N, 15.5%. Found: C, 72.8%; H, 11.9%; N, 15.5%.

Under an atmosphere of nitrogen a solution of 0.90 part of tetrakis(N-piperidino)ethylene in 17 parts of glyme was added dropwise with stirring to a solution of 1.02 parts (two molar proportions based on the amine) of TCNQ in 178 parts of warm glyme. The resulting precipitate was isolated by filtration and air-dried. There was thus obtained 0.04 part of the tetrakis(N-piperidino)ethylene/TCNQ charge transfer compound as a blue-black solid which decomposed at 243 C. and exhibited both a strong EPR absorption, i.e., was paramagnetic, and a wide spectral absorption band with a peak at 3.0a. Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

In the same manner there was obtained from 0.36 part of tetrakis(N-piperidino)ethylene in 17 parts of glyme and 0.184 part (one molar proportion based on the ethylene) of diphenoquinone in 65 parts of glyme, after filtration and drying, 0.05 part of the tetrakis(N-piperidino)ethylene/ diphenoquinone charge-transfer compound as a brown solid decomposing above 180 C. and exhibiting a strong EPR absorption. Image patterns made with the solid charge transfer compound were easily and accurately copied by the method described in Example 1.

Example XV A mixture of 26.8 parts of a,a-dimethoxytrimethylamine and 41.2 parts of anhydrous morpholine was heated in a glass reactor attached to a still as in Example XIII at the reflux in an oil bath at 98110 C. After 2.5 hours under these conditions, dimethylamine evolution ceased. Methanol was then distilled from the reaction mixture as the temperature of the bath was slowly raised over a period of four hours to 200 C. and held at that temperature for an additional 0.5 hour. Continued distillation under reduced pressure afforded 20.4 parts (42% of theory) of bis(morpholino)meth-oxymethane as a clear, colorless liquid boiling at 103-108" C. under a pressure corresponding to 1.01.2 mm. of mercury. On cooling, the product crystallized and melted at 6467.5 C. after recrystallization from methylcyclohexane.

Analysis.Calcd. for C H N O C, 55.5%; H, 9.3%; N, 13.0%. Found: C, 55.7%; H, 9.2%; N, 13.2%.

On cooling, the still residue from the isolation of the above bis(morpholino)methoxymethane solidified. There 7 was thus obtained 21.8 parts (41% of theory) of tetrakis (morpholino)ethylene. After recrystallization from ethyl acetate, the product melted at 170-171 C.

Analysis.Calcd. for C H gN O N, 15.2%. Found, N, 15.4%.

Under an atmosphere of'nitrogen a solution of 0.92 part of tetrakis (morpholino)ethylene in 18 parts of tetrahydrofuran was added dropwise to 1.02 parts (two molar proportions basedon the ethylene) of TCNQ in 89 parts of warm tetrahydrofuran. The resulting precipitate was isolated by filtration and air-dried. There was thus obtained 0.73 part of the tetrakis(morpholino) ethylene/TCNQ charge transfer compound as a blue-black solid which decomposed above 213 C. and exhibited both a strong EPR absorption, i.e., was paramagnetic, and a wide spectral absorption band with a peak at 3.0;. Dilute solutions in tetrahydrofuran or acetone were green in color. Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

Example XVI As in Example XIII, a mixture of 11.9 parts of a,a-

dimethoxytrimethylamine and 20.0 parts of N-methyl-' piperazine was heated at 130-210 C. until evolution of dimethylarnine and methanol had ceased. Continued distillation of the reaction mixture under reduced pressure afforded 7.8 parts (32% of theory) of bis[N-(N'-meth-, yl)piperazinyl]methoxymethane as a clear, colorless,

[N-(N'-methyl)piperazinyl1ethylene which after. recrystallization from acetonitrile melted at 79.0-80.5" C.

Analysis.-Calcd. for C H N N, 26.6%. N, 26.6%.

Under an atmosphere of nitrogen a solution of 1.05 parts of tetrakis[N-(N-methyl)piperazinyl1ethylene in 18 parts of tetrahydrofuran was added dropwiseto 1.02

Found:

parts (two molar proportions based on the ethylene) of TCNQ in 89 parts of warm tetrahydrofuran.

The result- 1 ing precipitate was isolated by filtration and air-dried.

There was thus obtained 0.42 part of the tetrakis [N- (N'- methyl)piperazinyl]ethylene/TCNQ charge transfer compound as an acetone-soluble, flufIy black solid which decomposed above 218 C. and exhibited both a strong EPR absorption, i.e., was paramagnetic, and a wide spectral absorption band with a peak at 3.014. solutions in tetrahydrofuran and acetone were green in color. paperwere accurately copied by the method described in Example I.

Dilute 1 Image patterns made: with the solid compound on In the same manner there was obtained from 0.84 part of tetrakis[N- (N'-methyl)piperazinyl]ethylene in 17 parts of glyme and 0.98 part (two molar proportions based on the ethylene) of tetrachloro-o-quinone, after filtration and drying, the vtetrakis[N-(N-methyl)piperazinyl] ethylene/tetrachloro o quinone charge transfer compound as a tan-colored. solid which rapidly became tacky in air. It exhibited a strong EPR absorption, i.e., was paramagnetic. Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

Example XVII liquid which boiled at 96-97" under; a pressure corresponding to 8mm. of mercury and which crystallized on cooling to a low-meltingsolid. This bicyclic tetrakis:

(disubstitutedamino)ethylene chemiluminesces strongly,

Solutions of the product in cyclohexane also cherniluminesce strongly in the presence.

in air with evolution of heat.

of air. I

Analysis.-Calcd. for C H5N C, 61.2%; H, 10.3%. Found: C, 61.2%; H; 10:5%.

Under an atmosphere of nitrogen a solutionof 0.98-

part of 1,1,3,3' tetrarmethyl-A -bi(imidazolidine) in 18 3 parts of tetrahydr-ofuran was added dropwise to 2.04

parts (two molar proportions based=on the'amine) of TIll''.

TCNQ in'155' parts of warm tetrahydrofuran. suiting precipitate wasisolated by filtration, and air-dried.

There was thus obtained.2.9 parts of the'1,1',3,3-tetra- 1 methyl A bi(imidazolidine) /TCNQ j charge transfer compound as an acetone-soluble, deep blue solid which decomposed above 220 C. and exhibiteda strong EPR i Asin Example XIII, a mixture of 87 parts of ecu-diirnethoxytrimethylamine and 85. parts of N,N'-diethylethylenediamine was heated under reflux in an oil bath at -105 C. until evolution ofdimethylamine became slow. Methanol wasv then distilled from; the :reaction mixture as the bath temperature :was slowly raised until a final temperature of 200 C; wasrea-ched. Continued distillation of the reactionamixture under reduced pressure afforded 69.5 parts (76% of theory) of l,1',3,3'-

tetraeLhyl-A -bi(imidazolidine) as a light yellow liquid boiling at 7982 C. under a pressure corresponding to 0.5 mm. of mercury. The product chemiluminesced strongly on exposure to air.

Analysis.-Calcd. for C H NL5C, 66.6%; H,11.2%; N, 22.2%. Found: C, 66.9%; H, 11.3%; N; 21.9%.

Under an atmosphere of nitrogen a solution of 0.475 part of 1,1, .3,3' rtetraethyl-A -bi(imid'azolidine) in 17.

parts of glyme was added dropwise with stirring over, a period of 30 minutes to a solution of 1.46 parts (3.1 molar proportions based on the amine) of chloranil in 86 parts of glyme.. The resulting. precipitate was. isolated by filtration and air-dried. There was thus obtained 1.55 parts of the 1,1,3,3'-tetraethyl-A -bi(imidazolidine)/ch1oranile charge transfer compound as .a bright green solid.

which decomposed above C. and exhibited a strong EPR absorption, i.e., was paramagnetic. Image pattern made with the solidcompoundon paper were accurately copiedby the method described in Example I.

In the same manner there was obtained from 0.95 part of 1,1,3,3'-tetraethyl-A '-bi(imidazolidine) in 18.parts of tetrahydrofuran and 1.53 parts: (two molar proportions based on the amine) of TCNQ in 133 parts of tetrahydrofuran, after filtration and dryin 2.71 parts of the 1,1',3,3 -tetraethyl-A '-bi(imidazolidine) /TCNQ charge transfer compound as a dark blue solid decomposing above C. and exhibiting a strong EPR absorption.

Image patterns made with the solid compoundwere easily and accurately copied by the method'described in Example .I.

In the same manner there was obtained from 0.24 part of l,1',3,3-tetraethyl-A -bi(imidazolidine) in 17 parts of glyme and 0.87part. (two molar proportions basedon the amine) of,tetra(p nitrophenyl)ethylene 'in' 86 parts'of glyme,.after filtration and air-drying,.the -l,1',3,3' tetraethyl A bi(imidazolidine)/tetra(p nitrophenyl)ethylene charge transfer compound as a reddish-brown solid;

which exhibited a strong EPR absorption, i.e., was paramagnetic,

ExamplegXlX A mixture of 23.8 parts of :a,a-dirnethoxytrimethylamine and 20.4 parts of NI-ethyl-N'-methylethylenedi-' amine was heated as in ExampleXIII to a bath temperature of 160 C. over a period of six hours, with the dimethylamine and methanol evolved in the reaction being removed by distillation. Essentially the theoretical quantity of the latter was obtained. Continued distillation of the reaction residue under reduced pressure afforded 17.2 parts (77% of theory) of l,'3'-diethyl-1,3-dimethyl-A '-bi(imidazolidine) as a light yellow liquid boiling at 8082 C. under a pressure corresponding to 0.25 mm. of mercury. The product chemiluminesced strongly on exposure to air.

Analysis.-Calcd. for CQH 4N C, 64.2%; H, 10.8%; N, 25.0%. Found;C,'64.'2%; H, 11I0%;N,'24.4%.

Underan atmosphere of nitrogen a solutiono'f 0.48 part of l,3-diethyl-1,3-dimethyl A "bi(imidazolidine) in 17parts of glyme was added dropwise' with stirring to a solution of 1.36 parts (two molar'proportions based on the amine) of 2,4,7 trinitro 9 fiuorenone in 65 parts of glyme. The resulting precipitate wasisolatedby filtration and air-dried. There was thus obtained 1.0 part of the 1,3 diethyl l,'3 dimethyl A bi(imidazolidine)'/2,4,7-trinitro 9-fluorenone charge transfer compound as an acetone-soluble, purple-black, fluffy solid which exhibited a strong'EPR absorption, i.e., was paramagnetic. Image patterns madewiththe solidcornpound on paper were accurately copied by-the method described in Example 1.

"Example XX A -mixture of 73.4 parts of a,a-dimethoxytrimethylamine, 62.6 parts of N,N-dimethyl-1,3-propanediamine, and 132 parts of benzene was heated atthe reflux with the benzene/methanol azeot-rope, boiling at 58 C. atatmospheric pressure, being removed continuously as -it was formed. The dimethylamine formed concurrently was ventedto-the atmosphere. Heating was continued until the azeotrope no longer distilled over and-the benzene was thenremoved by evaporative distillation. Continued distillationof the residue under reduced pressure afforded 208 parts (24% of theory) of 1,3-dimethyl-2- methoxyhexahydropyrimidine as a colorless liquid boiling at 6266 C. under a pressure corresponding to 25 mm. of mercury.

Analysis.Calcd. for C H N O: C, 58.3%; H, 11.2% N, 19.4%. Found: C, 58.6%; H, 11.2%; N, 19.4%.

Continued distillation of the reaction residue after removal of the 1,3-dimethyl-Z-methoxyhexahydropyrirnidine afforded 23.3 parts (34% of theory) of 1,l,3,3- tetramethyl-A -bi(hexahydropyrirnidine) as a light yellow liquid boiling at 104-105 C. under a pressure corresponding to 8.5 mm. of mercury. The product luminesced strongly on exposure to air.

Analysis.Calcd. for C gH N N, 25.0%. Found: N, 25.1%.

Under an atmosphere of nitrogen a solution of 0.23 part of 1,1,3,3' tetramethyl A bi(hexahydropyrimidine) in 18 parts of tetrahydrafuran was added dropwise with stirring to a solution of 1.27 parts (three'molar proportions based on the amine) of bromanil-in 89 parts of tetrahydrofuran. The resulting precipitate'was isolated by filtration and air-dried. There was thus obtained the 1,1',3,3' tetramethyl A bi(hexahydropyrimidine)/bromanil charge transfer compound as a greenish-tan solid which decomposed above 150 C. and exhibited a strong EPR absorption, i.e., was paramagnetic. Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

In a similar manner there was obtained from 0.56 part of l,1,3,3 -tetramethyl-A '-bi (hexahydropyrimidine) in '18 parts of tetrahydrofuran and 1.02 parts (two molar proportions based on the amine) of TCNQ in 89 parts of warm tetrahydrofuran, after filtration and drying, the 1,1',3,3 tetramethyl A bi(hexahydropyrimidine)/ TCNQ charge transfer compound as a blue-black solid which decomposed above 235 C. Dilute acetone solutions were bright green colored. It exhibited both a strong EPR absorption, i.e., was paramagnetic, and a wide spectral absorption band with a speak at 3.0 Image patterns made with the solid compound on paper were accurately copied by the method described in Example I.

As stated above, the charge transfer compounds of the tetrakis(dialkylamino)ethylenes can be formed with any Lewis acid. amples just given, charge transfer compounds can be prepared from many other Lewis acids, of which wide In addition to the fully detailed exnumbers are known. For instance, when methylene dichloride solutions of TMAE and maleic anhydride were mixed, the mixture turned red immediately with evolution of heat and apparent further reaction. When methylene dichloride solutions of TMAE and tetrachlorobenzoquinone were mixed, a blue-green precipitate formed which exhibited an intense EPR absorbance. The supernatant blue solution and the blue-green precipitate exhibited separately no EPR absorption after about two hours. -Presumably subsequent reaction of the charge transfer compound occurred. When methylene dichloride solutions of TMAE and TCNE were mixed in a different ratio than given in Example IV, a clear red solution was obtained which exhibited an intense EPR absorbance which! persisted, apparently undim-inished, for 72 hours. The colored charge transfer compound was thus strongly paramagnetic. When methylene dichloride solutions of TMAE and indanetrione, i.e., triketohydrindene, were mixed, the mixture turned red immediately and a dark precipitate subsequently'formed. The solid was intensely paramagnetic.

When TMAE and acrylonitrile were mixed, a redcolored solution resulted which exhibited an EPR absorbance. When TMAE and tetrachloroethylene were mixed, the mixture turned yellow, but no EPR absorbance was exhibited. Similar results were obtained with TMAE and styrene. In these two latter instances, the

charge transfer compounds formed were presumably diamagnetic in the ground state.

Solutions of TMAE and hexachloro-1,3,5-cyclohexanetrione formed a red-orange precipitate with concomitant evolution of heat. The solid exhibited an EPR absorbance.

When alcohol solutions of TMAE and riboflavin were mixed, a brilliant red-colored solution resulted which gave an intense EPR signal.

The present invention is generic to the charge transfer complexes between the tetrakis(dialkylamino)ethylenes and pi or Lewis acids broadly. 'Ilhe pi acids involved will normally have at least one carbon atom multiply bonded to another atom, generally another carbon atom or an oxygen, nitrogen, or sulfur atom. A

particularly'nsefulclass of the pi acids are those wherein at least one carbon is multiply bonded to another carbon, such as in an ethylenic group or in a benzene or other carbocyclic or heterocyclic aromatic nucleus. Especially outstanding amongst these pi acids, wherein at least one carbon is multiply linked to another carbon, are those compounds wherein at least one of the carbons involved in the multiple linkage carries at least one electronegative substituent. These electronegative substituents are recognized and described as such in the literature and are frequently also referred to as substituents which, when present on ring carbon of an aromatic nucleus,tend to direct any entering substituent radical into the meta-position, i.e., the so-called meta-orienting groups. These substituents have also been described by Price, Chem. Rev. 29, 58 (1941), in terms of the electrostatic-polarizing force measured in dynes of the said substituent groups on an adjacent double bond of a benzene nucleus. Quantitatively, any substituent which has or exhibits an electrostatic polarizing force in dynes greater than 0.50 is classed as electronegative and metaorienting. These substituents include nitroalkyl, such as 2-nitropropyl, nitromethyl; polyhaloalkyl, such as diof such 1 complexes.

chloro-methyl, trichloromethyl, trifluoromethyhfnitroso .and nitro; ammonium and quaternary ammonium: and

ammonium alkyl and quaternary ammonium alkyl, such as ammonium, methyl quaternary trimethylammonium,

ammonium, and quaternary trimethylammonium'methyl;

carbamoyl and substituted carbamoyl; carbacyl, such as 1 acetyl and formyl; polycyanoalkyl, such as dicyanomethyl; hydrocarbyloxycarbonyl, such as carbonyl, and other carbacyl esters; carboxyl and. sulfo and other acyl groups; hydrocarbyl sulfonyl, such as methylsulfonyl, and other sulfonic acid esters; formyl, acetyl, propionyl, and other carbacyl groups; and nitrile.

methoxy- In accordance with the present invention, it has been found that reaction of any tetrakis(dialkylamino)ethylene with any pi or-lew-is acid produces charge transfer compoundsawhich are characteristically colored. The reaction takes place upon merely mixing the reactants alone orin an inert sol-vent or solvents. Any convenient 1 temperature can be used, but low temperatures sometimes are desirable to avoid or suppress other reactions. In those instances wherein the pi acid is. a solid, the charge transfer compound can be made by simply mixing the solid with the liquid or solid tetrakis(dialkylamino)ethylone and suitably mixing. If desired, the reaction mixture can be heated slightly. In those instances. wherein the pi acid is a liquid, the liquid can be mixedwith the liquid or solid tetrakis (dimethylamino)et-hylene. In those the complex tends to be protected from further attack by excess Lewis acid or base. The charge trans-fer com: plexes can be purified by a' variety of procedures depend-J ing on the stability and solubility of the individual complexes. Theseinclude solution and precipitation from suitable solvents, sublimation, and zone refining.

The tetrakis(dialkylamino)ethylene charge transfer compoundswith the stronger pi acids are paramagnetic and thus have usefulness in recognized applications for paramagnetic materials. These paramagnetic complexes are .generically characterized by exhibiting paramagnetic absorption in the electron paramagnetic resonance spectrum (EPR absorption). 7

A stillfurther use of the -tetrakis(dialkylamino)ethylene charge transfer compounds which are paramagnetic resides in an additional characteristic physical property Thus, these paramagnetic .tetrakise (dialkylamino)ethylene compounds exhibit strong, broad absorption in the near infrared region, e.g., from 0.5 ;to 2.0 microns, generally centered around 1.0 micron. Based on this property, such complexes findsignificant use vas the coloring agent, or pigment, in writing inks which will permit reproduction of textmatter by thermographic, processes.

'Thermographic copying represents a convenient and easy. method of rapidly copying text material dry. How? ever, operability of the process requires that the text' material to be copied musta-bsorb in the infrared. Othe-r- Printed material, i

sorbin the infrared. The same is true of typewritten matter, whether it be the original copy or carbon copies thereof sinceagain-the text matter is defined by carbon fountain pen inks, and in particu-la'rballpoint inks, achieve their characteristic; color th-roughithe :uselof dyes or pig ments which do not absorb inzthe infrared but onlyin the visible; Accordingly, textmatter appearin-gin these I types of inks cannotibe copied by' a thermographic vprocess. The paramagnetic tet-rakis(dialkylamino)ethylene 3 charge transfer complexes in absorbing in the nearinfrae redpermit direct, ready,.and easy. thermographic, copying I of lettertextv matter defined lby; inks carrying these com-v plexes as.t-he coloring, or pigment-ing, agent..

All the tetrakis(dialkylamino)ethylene charge transfer pi complexes, including ;bothv the diamagnetic and paramagnetic types, .aregenerically; colored and'accordingly; find use in any of the. many well-known :and established V uses for colored materials. Thus, in the case of colored,

solutions, obtainable with quite weakpi acids-,eg, nitrobenzene, theseare useful. in obtaining decorative :color effects. In the case of the,tetrakis(dialkylamino)ethylene charge transfer picomplexes; with stronger. pi acids; ;the

complexes are colored :solids irrespective .ofwhether the complex is paramagnetic or not. Thesci colored solid complexes find use in any of the many well-established fields, such as dyes, pigments,.for both ,paintsza'nd plastics,

and colored fillersafor theilattert' Since all the rtetrakis(dialkylamino)ethylene charge. 7 transfer complexes are .colored, the controlled formation: 7

thereof forms the tbasis'for. still another use, viz.,- the; re-

production oftext matter by impact printing, i.e.,Iby the. pressure formation of graphic image'snfTliugone sheet 'of a carrier, e.g., paper; is iinpregnatedwith a solution of tetrakis(dialkylamino)ethylene :and the solvent removed. via evaporation, leaving the ,tetrakis(dialkyla'n1ino)e-thyl- 1 ene deposited in, on, and .thnough thetpaper carrier. An-f other separatesheet of paper is similarly so treated with'a pi acid. A laminate of. the. two sheets will reproduce .a

colored image in the second-sheet made'by pressure .0111:

the first sheet;

As stated andillustrated in the foregoing, this inven-' tion is generic to thechargetransfer compounds of .the

tetrakis(dialkylamino)ethylenes and Lewis acids broadlyt. The tetrakis(dialkylamino)ethylenes is.' intendedto. in-- clude those compounds not only where there are two :dis: crete, i.e., separate, substituents'aliphatic! in character (i.e., aliphatic and cycloaliphatic.) on each amino nitro- 1 gen but also those wherein two'substituents on individual or adjacent nitrogens are embodied in' 'a single divalent radical, making with the amino nitrogen a monoaza, di- F 1 aza, and/or oxa/aza'heterocycle of -fromthree to seven V total ringmembers wherein any substituents onrring'j members are solely .saturatedphydrocarbon of; no more than eight-carbons eachi Thusythe said term describes not only the simple tetrakis(dialkylamino)ethylenes but. 7 also the more complicated structures wherein:substitu ents on individual or adjacentamino nitrogen are together joined pairwise,either directly. or through intervening heterocyclic oxa or aza members, The :first memberof stituting the requisite different secondary amine.

The other. ,tetrakis(dialkylaminqkthylenes' needed as; intermediates for preparing. the 1 charge transfer compounclsof the present invention are-newc'ornpounds and-E can be prepared by the, interaction between the.=requisite"' secondaryamine and the hydrocarbon"amidefacetals;

whichmay also be described as disubstituted aniinodihydrocarbyloxymethanes, preferably those of t relatively short chain:length,*in the. manner disclosed and claimed V in theapplication of Winb,erg,QSerial-No. 91,589,1filed concurrently herewith and now abandoned but rcfiled as the continuation-in-part application Serial No. 174,404, on February 20, 1962. This interaction between the requisite'secondary amine and amide acetal intermediates, i.e., the disubstituted amino-1,1-dihydrocarbyloxymethanes, is basically a substitution or substitution/condensation reaction in which the entering secondary amine moiety is substitutcd for the disubstituted amino moiety of the amide acetal and also for one ofthe hydrocarbyloxy moieties of the amide acetal and with ultimate splitting out of another molecule of the hydroxyhydrocarbyl compound and resultant dimerization to the formation of the desired'tetrakis(dialkylamino)ethylene, all in accord with the following stoichiometry:

'wherein-the Rs, which can be alike or different, are

monovalent alkyl or cycloalkyl radicals, generally of no more than eight carbons each, which can be together joined to form with the intervening nitrogen a heterocan also be alike or different, or together joined, are

-monovalent alkyl, aryl, aralkyl, alkaryl, -or cycloalkyl radicals and, when together joined, form with the two -oxygens and intervening carbon a 1,3-dioxaheterocycle of from five to seven ring members; and the Rs, which can also be alike or different or together joined pairwise on the same or different nitrogens, are monovalent alkyl or cycloalkyl hydrocarbon or oxaand/orazahydrocarbon radicals of no more than eight carbons each. In any event, when the two R"s are together joined, they form with the indicated amine nitrogen a monoazacarbocycle, an oxaazacarbocycle, or a diazacarbocycle of from three to seven ring members.

Because of easier conversion to the desired tetrakis(dialkylamino)ethylenes, the short chain hydrocarbon amide acetals are preferred wherein the radicals pendent on the nitrogen and the two oxy oxygens are shont chain, saturated hydrocarbon, and oxaand azahydrocarbon radicals of no more than six chain or ring members each. Ideally speaking, the best amide acetal intermediate is the one where all such radicals are the shortest, viz., 1,1-

dimethoxydimethylaminc, i.e., the dimethyl acetal of N,N-dimethylformamide. The reaction is effected simply by mixing the two coreactants, generally with the secondary amine in excess, and heating to drive off the hydroxyhydrocarbyl compound, i.e., alcohol or phenol, and amine formed in accord with the foregoing stoichiometry.

Thus, the resulting substituted secondary amine corresponding to the secondary amino moiety of the amide acetal coreactant will be removed'by distillationv as the reaction proceeds, as will any resulting alcohol or phenol, through the condensanon/substitution of the second disubstituted amino fragment from the entering secondary amine for one of the hydrocarbyloxy fragments of-the amide acetal. The final dimerization step is effected substantially solely thermally, and in order to'insure maximum yield of the desired tetrakis(dialkylamino)ethylenes, the reaction willfinally be carried out in the temperature range 125-250 C., except in those instances where shortchain diamines are the entering secondary amines, resulting in the formation of cyclic tetrakis-substituted aminoethylenes, inv which instance reaction temperatures need not normally be carried much above the 80425 C. range.

The reaction is an easy one to carry out, requiring only that the necessary two coreactants be brought together and heated. To avoid possible side reactions and other complicating factors, the reaction is normally carried out in a dry, inert atmosphere, e.g., dry N The substituted secondary amine corresponding to the disubstitutedamino moiety of the starting amide acetal coreactant will normally be removed by simple distillation. Ideally speaking, this disubstituted amine will be sufficiently lowboiling that it can be permitted to vent as a gas through the reflux condenser of the distallation head normally used. The alcohol or phenol resulting from the densation reaction between a second molar proportion of the entering secondary amine and one of the hydrocarbyloxy moieties of the amide acetal coreactant will normally be condensed and'removed as a liquid distillate as formed.

While no reaction solvent at all is required, for ease and convenience it may sometimes be desirable to use an inerthydrocarbon or hydrocarbon ether solvent in ex- 'cess to assure good contact between the two coreactants. 'Sincer'nany of the lower alcohols form azeotropes with various of the hydrocarbon solvents, it frequently develops that the alcohol/hydrocarbon solvent azeotrope simply is distilled from the reaction mixture, and when azeo- Y trope formation ceases, the reaction for the formation of the bis(disubstitutedamino)hydrocarbyloxymethane is substantially complete. Under such conditions, i.e.,using an inert solvent, the reaction mixture normally will not reach'the temperatures necessary for the formation of the tetrakis(disubstitutedamino)ethylenes except, as mentioned'before, for the diamines and resultant cyclic amino- 'et-hylenes. For the tetrasubstituted'products, either no reactiOndiluent isused and the reaction is'driven to completion solely thermally,or for convenience, an inert reaction solvent is-used and the reaction driven to completion-therewith to the formation of the bis(disubstitutedamino)hydrocarbyloxymethane. The reaction diluent will then be removed by distillation and the tetrakis(disubstitutedamino)ethylene formed by further heating of the bis(disubstitutedamino)hydrocarbyloxymethane.

The requisite amide acetal intermediates can be prepared by the method of Meerwein, Angew. Chem. 71,530

(1 959), by reaction between a hydrocarbon ether, a hydrocarbyl fluoride, and silver fluoborate to form a trihy- -drocarbyloxonium fluoborate which is then reacted with the requisite N,N-dihydrocarbyl-substituted carboxamide to form the intermediate oxonium fluoborate derivative of thearnide, i.e., an u-(N,N-dihydrocarbylamino)-a-(hydrocarbyloxy)hydrocarbonium fluoborate, which is subsequently further reacted with an alkali metal alcoholate to form the desired amide acetal and, as a co-product, the alkali metal fluoborate. Also, as disclosed in the same reference, the intermediate higher amide acetals can be prepared by alcohol exchange with the lower amide acetals in accord with the following stoichiometry:

plies to any desired higher hydrocarbylamino amide acetals in'whic-h an amine exchange reaction in accord with the following stoichiometry will serve to prepare any desired higher hydrocarbylamino amide acetals:

where R is of greater carbon content than R.

In both these alcohol and amine exchange reactions, the cyclic products can also be obtained, i.e., by the use of a glycol to obtain the cyclic hydrocarbyloxy moiety or by use of a cyclic secondary amine to obtain the cyclic amino moiety of the amide acetals.

se ame 15 The preferred method of preparing the necessary intermediate amide acetals involves the reaction of an alkali metal of alkaline earth metal'salt of the desired alcohol or phenol with the requisite u,a-dihalosubstituted tertiary amine in accord with the following stoichiometry:

' OR 'l R i+ mM(OR)n 'mMX" HON i a wherein the Rs, which can be alike or different, are monovalent alkyl or cycloalkyl radicals of nomore than 8 carbons each, which can be together joined to form a 1 saturated monoaza, diaza, or oxaza heteroeyele of v3-7 ring members; the Xs, which can be alike or different, are

halogens of atomic No. from 935;'M is an alkali;metal or an alkaline earth metal; R is a monovalent alkyl,

aryl, aralkyl, alkaryl, or cyeloalkyl radical of no more than 8 carbons; and m and n are integers from 1-2, inelusive, depending on the valence of the metal Mland such that m+n=3.

When n is 2, the R radicals can be together joined to form with the intervening carbon and two oxygens a 1,3-dioxaearbocyele of 5 to 7 ring mem- -bers. This preferred synthesis of the intermediates forms the subject matter of Brown U.S. Patent 3,092,637.

In additiontto the aforesaid new tetrakis(disubstitutedamino)ethylenes and the necessary amide acetal and .secondary amine eoreactant-s given in the foregoing detailed examples, other such coreactants of these same; generic types can be so similarly used to give still further amino ethylene intermediates for the charge transfer compounds of the present broad product inventions Thus, there can be used such other formamide acetals as N-(dimethoxymethyl)-N-methyl-n-octylamine, N-diethoxymethyldiisobutylamine, N-diethoxymethyl-N-ethyl-p-toluidine, N diethoxymethylpyrrolidine, N-diisopropoxymethymorpholine, and the like. In preparing the new tetrakis(disubstitutedamino)ethylenes there can be used such cyclic secondary amines as ethyleneimine, i.e., aziridine, azetidine, i.e., azaeyelobutane, perhydroazepine, A -pyrroline,

i.e., 2,5 dihydroazoline, 1,-2,2-trimethylhydrazine, and the,

like. Reaction of these additional amine species with the I dimethyl ace-tal of N,-dimethylformamide results, respectively, in the formation of the following tetrakis(cyclic l-aziridinyl ethylene, 1,1,2,2-tetrakis( 1-azetidinyl)ethylene, 1,1,2,2 tetrakis(1 hexahydroazepinyl)ethylene, 1,l,2,2 tetrakis( 1,2,5 dihydroazolinyl)ethylene, i.e., 1,1,2,2-tetrakis( l-A -pyrrolinyl ethylene, 1,1,2,2-tetrakis [1-(1,2,2-trimethylhydrazinyl)]ethy1ene, and the like.

Since obvious modifications andlequiva-lentsin the invention will be evident'to those skilled in the chemical arts, I propose to be boundisolely by thetappended claims.

The embodiments of the invention in which an exand acyclic disubstitutedamino)ethylenes: 1,1,2,2-tetrakis elusive property or privilege is claimed ar'e defined ias follows:

1; A charge vtransfer complex of (1) anyamin'o com: pound of the formula B z/IN wherein the Rs are selected fromtthe group consisting,

individually, or monovalentalkyl'and cyeloalkyl hydrocarbon of up to 10 carbons, jointly on-eaeh nitrogen, of divalent alkylene, eyeloalkylene and oxa-" and azahydrocarbon of up to 10 carbons and forming a heterocyelic structure '0f3-7 ring members, and, jointly on adjacent nitrogens, of divalent alkylen'e, cyeloalkylene and oxaand azahydroearbon of up to 10 carbons andforming a heterocyclic structure of 3-7 ring members and (2)] an organic 'Lewis acid containing at least onemultiple bond.

between carbon and a member Of the group consisting of carbon, nitrogen, oxygen and sulfur, the ,mole of (1) to (2) being betweenlzland 1:10. I

-2..\The complex of claim 1 whereinzthe amino com; 1

pound is tetrakis(di-methylamino.)ethylene."

3. A charge transfer complex of an amino of claim 1 andchloranil.

4. A charge transfer complex of an, amino compound of claim 1 and bromanil.

5.- A charge transfer complex of :an amino of claim 1 andliodanil.

6; A charge jtransfer complex of an amino eompound compound 12. A charge transfer complex of'an :amino compound of claim 1 and p-tricyanovinyl-N,N-dirnethylaniline.j

13. The complex of clai-m l wherein the amino'compound is tetrakis(N-pyrrolidinyl)ethylene, 1 I

14. The complex of claim'l wherein;the,arnino com-.

pound is tetrakis(N-pip'eridino)ethylene.-

15. The complex of elaim'l whereinthe Taminoconr, pound is tetrakis(morpholino)ethylene. v

16. The complex of claim =-1 wherein the pound is tetrakis[N (Nfmethyl)piperazinyl]ethylene;

17. The complex of claim 1 wherein ,the amino com-t poundis 1,1';3,3-tetramethyl-A '2'-bi(imidazolidine) 18. The complex of claim 1 wherein he amino compound is 1,1',3,3'-tetraethyl-AZ -bi(imidazolidine)t 19. The complex of claim'l wherein :the aminq com-t bi(imidazolidine) l V 20 The complex 'of claim- 1 wherein athelamino ,eo'ma pound is 1,1';3,3'-tetramethyl-A -bi(hexahydropyrimidine).

21. A chargeatransfercomplex of an aminoeompound j of claim 1 and a quinone. i

22. A charge ,:transfer complex, of: tetrakis (dimethylamino)ethylene and a quinone.-- I 23. =Acharge, transfer complex :of tetrakis(dimethyl-. amino)ethylene and ch-loranil.

24. A charge transfer complex ofv ftetrakis(diriiethyl+ amino)ethylene and bromanil.

25.=A' eharge transfer complex ,a of tetrakistdimethylamino)ethylene and iodanil.

26. A charge, transfer complex? of, tetrakis(dimethyl.-

amino)ethylene and te-trabromo-1,2 benzoquinone- 27.'A charge ;%transfer complex of, tetrakis(dimethylg I amino)ethylene and diphenoquinone..

28. A charge transfer :eomplex of 'tetrakis(dimethyl amino)ethylene and tetraeyanoethylene.

29. A charge transfer complex ofv ttetrakis(dimethylamino)ethylene and m-dinitrobenzeneuz 30. A chargetransfer complex, of ,!tetrak;is(dir'nethyl amino)ethylene and hexachlorocyelopentadiene.

31'. A charge transfer complex of ftetrakis (dimethyl-lamino)ethylene and dichlo'rofumaronitrilex 32.i A charge 1 transfer complex' of ,tetrakis(dimethyl amino)ethylene and p-tricyanovinyl=N,N dimethylaniline.; 33. A charge transfer. ;cornplex iof' tetrakis Nf-pyrroli-r dinyl)ethylene and 7,7,8,8 tetracyanoquinodimethane v 34.A charge transfer complex of -tetrakis(-Nkpiperidino)ethylene and diphenoquinone; 7

No references cited; l

WALTER A; MODANCE,-Pr'imary Examiner. r

IRVING MARCUS,"L. DQROSDOL, Examiners. I i

ratio compound compound compound amino .ieom- 

1. A CHARGE TRANSFER COMPLEX OF (1) AN AMINO COMPOUND OF THE FORMULA
 15. THE COMPLEX OF CLAIM 1 WHEREIN THE AMINO CONPOUND TETRAIS (MORPHOL) ETHYLENE. 